Method of polymerization and polymer produced therefrom

ABSTRACT

A polymer produced by a polymerization process, in the gas or slurry phase, with a liquid carrier comprising an activator and a metal catalyst compound comprising a group 3 to 14 metal atom bound to at least one anionic leaving group and also bound to at least two group 15 atoms, at least one of which is also bound to a group 15 or 16 atom through another group which may be a C 1  to C 20  hydrocarbon group, a heteroatom containing group, silicon, germanium, tin, lead, phosphorus, or a halogen, wherein the group 15 or 16 atom may also be bound to nothing or a hydrogen, a group 14 atom containing group, a halogen, or a heteroatom containing group, and wherein each of the two group 15 atoms are also bound to a cyclic group and may optionally be bound to hydrogen, a halogen, a heteroatom or a hydrocarbyl group, or a heteroatom containing group.

CROSS-REFERENCE TO RELATED APPLICATIONS

[0001] The present application is a Divisional of U.S. application Ser.No. 09/442,813, filed Nov. 18, 1999, now issued as U.S. Pat. No. ______.

FIELD OF THE INVENTION

[0002] This invention relates to olefin polymerization catalystscontaining a metal atom bound to at least two group 15 atoms fed insolution or slurry into a gas phase or slurry phase reactor to producepolyolefins and the polyolefins produced therefrom.

BACKGROUND OF THE INVENTION

[0003] Metallocene polymerization catalysts (i.e. transition metals,typically groups 4, 5 or 6, having at least one pi bonded ligand,preferably a cyclopentadienyl, indenyl or fluorenyl group) have recentlybeen used to produce resins having a desirable product properties.

[0004] Furthermore, there is always a need in the art for a method tointroduce catalysts into a gas or slurry phase reactor in such a way asto reduce fouling and/or increase activity. Catalysts used in the gasphase are typically supported because in the past liquid catalystsseverely fouled the reactor. Some supported catalysts however have thedisadvantages of reduced activity. Thus there is a need in the art ofgas or slurry phase processes to find efficient, cost effective reducedfouling means to feed catalysts into a gas or slurry phase reactor. Formore information on the disadvantages of using liquid catalysts in a gasphase reactor see the background sections of U.S. Pat. No. 5,317,036 andU.S. Pat. No. 5,693,727 which relates to introducing unsupportedcatalysts into a gas phase reactor.

[0005] Schrock et al in US 5, 889,128 discloses a process for the livingpolymerization of olefins in solution using initiators having a metalatom and a ligand having two group 15 atoms and a group 16 atom or threegroup 15 atoms. In particular, the solution phase polymerization ofethylene using {[NON]ZrMe}[MeB(C₆F₅)₃] or {[NON]ZrMe(PhNMe₂)]}[B(C₆F₅)₄]is disclosed in examples 9 and 10.

[0006] Mitsui Chemicals, Inc. in EP 0 893 454 A1 discloses transitionmetal amides combined with activators to polymerize olefins in thesolution phase. EP 893 454 A1 discloses unsupported transition metalamide compounds used in combination with activators to polymerizeolefins in the solution phase.

[0007] Ethylenebis(salicylideneiminato)zirconium dichloride combinedwith methyl alumoxane deposited on a support and unsupported versionswere used to polymerize ethylene by Repo et al in Macromolecules 1997,30, 171-175.

[0008] U.S. Ser. No. 09/312,878, filed May 17, 1999 discloses novelsupported catalysts used in the gas or slurry phase to polymerizeolefins.

SUMMARY OF THE INVENTION

[0009] This invention relates to a catalyst system comprising a liquidcarrier, an activator and a metal catalyst compound comprising a group 3to 14 metal atom bound to at least one anionic leaving group and alsobound to at least two group 15 atoms, at least one of which is alsobound to a group 15 or 16 atom through another group which may be a C₁to C₂₀ hydrocarbon group, a heteroatom containing group, silicon,germanium, tin, lead, phosphorus, or a halogen, wherein the group 15 or16 atom may also be bound to nothing or a hydrogen, a group 14 atomcontaining group, a halogen, or a heteroatom containing group, andwherein each of the two group 15 atoms are also bound to a cyclic groupand may optionally be bound to hydrogen, a halogen, a heteroatom or ahydrocarbyl group, or a heteroatom containing group.

[0010] This invention relates to the gas or slurry phase polymerizationof olefins using an olefin polymerization catalyst system comprising anactivator, a liquid carrier and a transition metal compound as describedbelow.

[0011] The activator is preferably an aluminum alkyl, an alumoxane, amodified alumoxane, a non-coordinating anion, a borane, a borate or acombination thereof.

[0012] The carrier is preferably an alkane.

DETAILED DESCRIPTION OF THE INVENTION

[0013] In a preferred embodiment the activator is combined with acompound represented by the formulae:

[0014] wherein

[0015] M is a Group 3 to 12 transition metal or a Group 13 or 14 maingroup metal, preferably a Group 4, 5, or 6 metal, and more preferably aGroup 4 metal, and most preferably zirconium, titanium or hafnium,

[0016] each X is independently a leaving group, preferably, an anionicleaving group, and more preferably hydrogen, a hydrocarbyl group, aheteroatom or a halogen, and most preferably an alkyl.

[0017] y is 0 or 1 (when y is 0 group L′ is absent),

[0018] n is the oxidation state of M, preferably +3, +4, or +5, and morepreferably +4,

[0019] m is the formal charge of the YZL or the YZL′ ligand, preferably0, −1, −2 or −3, and more preferably −2,

[0020] L is a Group 15 or 16 element, preferably nitrogen,

[0021] L′ is a Group 15 or 16 element or Group 14 containing group,preferably carbon, silicon or germanium,

[0022] Y is a Group 15 element, preferably nitrogen or phosphorus, andmore preferably nitrogen,

[0023] Z is a Group 15 element, preferably nitrogen or phosphorus, andmore preferably nitrogen,

[0024] R¹ and R² are independently a C₁ to C₂₀ hydrocarbon group, aheteroatom containing group having up to twenty carbon atoms, silicon,germanium, tin, lead, or phosphorus, preferably a C₂ to C₂₀ alkyl, arylor aralkyl group, more preferably a linear, branched or cyclic C₂ to C₂₀alkyl group, most preferably a C₂ to C₆ hydrocarbon group.

[0025] R³ is absent or a hydrocarbon group, hydrogen, a halogen, aheteroatom containing group, preferably a linear, cyclic or branchedalkyl group having 1 to 20 carbon atoms, more preferably R³ is absent,hydrogen or an alkyl group, and most preferably hydrogen

[0026] R⁴ and R⁵ are independently an alkyl group, an aryl group,substituted aryl group, a cyclic alkyl group, a substituted cyclic alkylgroup, a cyclic aralkyl group, a substituted cyclic aralkyl group ormultiple ring system, preferably having up to 20 carbon atoms, morepreferably between 3 and 10 carbon atoms, and even more preferably a C₁to C₂₀ hydrocarbon group, a C₁ to C₂₀ aryl group or a C₁ to C₂₀ aralkylgroup, or a heteroatom containing group, for example PR₃, where R is analkyl group,

[0027] R¹ and R² may be interconnected to each other, and/or R⁴ and R⁵may be interconnected to each other,

[0028] R⁶ and R⁷ are independently absent, or hydrogen, an alkyl group,halogen, heteroatom or a hydrocarbyl group, preferably a linear, cyclicor branched alkyl group having 1 to 20 carbon atoms, more preferablyabsent, and

[0029] R* is absent, or is hydrogen, a Group 14 atom containing group, ahalogen, a heteroatom containing group.

[0030] By “formal charge of the YZL or YZL′ ligand”, it is meant thecharge of the entire ligand absent the metal and the leaving groups X.

[0031] By “R¹ and R² may also be interconnected” it is meant that R¹ andR² may be directly bound to each other or may be bound to each otherthrough other groups. By “R⁴ and R⁵ may also be interconnected” it ismeant that R⁴ and R⁵ may be directly bound to each other or may be boundto each other through other groups.

[0032] An alkyl group may be a linear, branched alkyl radicals, oralkenyl radicals, alkynyl radicals, cycloalkyl radicals or arylradicals, acyl radicals, aroyl radicals, alkoxy radicals, aryloxyradicals, alkylthio radicals, dialkylamino radicals, alkoxycarbonylradicals, aryloxycarbonyl radicals, carbomoyl radicals, alkyl- ordialkyl-carbamoyl radicals, acyloxy radicals, acylamino radicals,aroylamino radicals, straight, branched or cyclic, alkylene radicals, orcombination thereof. An aralkyl group is defined to be a substitutedaryl group.

[0033] In a preferred embodiment, L is bound to one of Y or Z and one ofR¹ or R² is bound to L and not to Y or Z.

[0034] In an alternate embodiment R³ and L do not form a heterocyclicring.

[0035] In a preferred embodiment R⁴ and R⁵ are independently a grouprepresented by the following formula:

[0036] wherein

[0037] R⁸ to R¹² are each independently hydrogen, a C₁ to C₄₀ alkylgroup, a heteroatom, a heteroatom containing group containing up to 40carbon atoms, preferably a C₁ to C₂₀ linear or branched alkyl group,preferably a methyl, ethyl, propyl or butyl group, any two R groups mayform a cyclic group and/or a heterocyclic group. The cyclic groups maybe aromatic. In a preferred embodiment R⁹, R¹⁰ and R¹² are independentlya methyl, ethyl, propyl or butyl group, in a preferred embodiment R⁹,R¹⁰ and R¹² are methyl groups, and R⁸ and R¹¹ are hydrogen.

[0038] In a particularly preferred embodiment R⁴ and R⁵ are both a grouprepresented by the following formula:

[0039] These metal compounds are prepared by methods known in the art,such as those disclosed in EP 0 893 454 A1 and U.S. Pat. No. 5,889,128and the references cited therein which are all incorporated by referenceherein. A preferred direct synthesis of these compounds comprisesreacting the neutral ligand with M^(n)X_(n) (M is a group 3-14 metal, nis the oxidation state of M, X is an anionic group, such as halide, in anon-coordinating or weakly coordinating solvent, such as ether, toluene,xylene, benzene, methylene chloride, and/or hexane or other solventhaving a boiling point above 60° C., at about 20 to about 150° C.(preferably 20 to 100° C.), preferably for 24 hours or more, thentreating the mixture with an excess (such as four equivalents) of analkylating agent, such as methyl magnesium bromide in ether. Themagnesium salts are removed by filtration, and the metal complexisolated by standard techniques.

[0040] In a preferred embodiment this invention relates to a method toprepare a metal compound comprising reacting a neutral ligand with acompound represented by the formula M^(n)X_(n) (where M is a group 3-14metal, n is the oxidation state of M, X is an anionic leaving group) ina non-coordinating or weakly coordinating solvent, at about 20° C. orabove, preferably at about 20 to about 100° C., then treating themixture with an excess of an alkylating agent, then recovering the metalcomplex. In a preferred embodiment the solvent has a boiling point above60° C., such as ether, toluene, xylene, benzene, methylene chlorideand/or hexane.

[0041] The transition metal compounds described herein are preferablycombined with one or more activators to form an olefin polymerizationcatalyst system. Preferred activators include alkyl aluminum compounds(such as diethylaluminum chloride), alumoxanes, modified alumoxanes,non-coordinating anions, boranes, borates and the like. It is within thescope of this invention to use alumoxane or modified alumoxane as anactivator, and/or to also use ionizing activators, neutral or ionic,such as tri (n-butyl) ammonium tetrakis (pentafluorophenyl) boron or atrisperfluorophenyl boron metalloid precursor which ionize the neutralmetallocene compound. Other useful compounds include triphenyl boron,triethyl boron, tri-n-butyl ammonium tetraethylborate, triaryl boraneand the like.

[0042] There are a variety of methods for preparing alumoxane andmodified alumoxanes, non-limiting examples of which are described inU.S. Pat. No. 4,665,208, 4,952,540, 5,091,352, 5,206,199, 5,204,419,4,874,734, 4,924,018, 4,908,463, 4,968,827, 5,308,815, 5,329,032,5,248,801, 5,235,081, 5,157,137, 5,103,031, 5,391,793, 5,391,529,5,693,838, 5,731,253, 5,041,584 and 5,731,451 and European publicationsEP-A-0 561 476, EP-B1-0 279 586 and EP-A-0 594-218, and PCT publicationWO 94/10180, all of which are herein fully incorporated by reference.

[0043] Ionizing compounds may contain an active proton, or some othercation associated with but not coordinated to or only looselycoordinated to the remaining ion of the ionizing compound. Suchcompounds and the like are described in European publications EP-A-0 570982, EP-A-0 520 732, EP-A-0 495 375, EP-A-0 426 637, EP-A-500 944,EP-A-0 277 003 and EP-A-0 277 004, and U.S. Pat. Nos. 5,153,157,5,198,401, 5,066,741, 5,206,197, 5,241,025, 5,387,568, 5,384,299 and5,502,124 and U.S. patent application Ser. No. 08/285,380, filed Aug. 3,1994, all of which are herein fully incorporated by reference. Otheractivators include those described in PCT publication WO 98/07515 suchas tris (2,2′,2″-nonafluorobiphenyl) fluoroaluminate, which is fullyincorporated herein by reference. Combinations of activators are alsocontemplated by the invention, for example, alumoxanes and ionizingactivators in combinations, see for example, PCT publications WO94/07928 and WO 95/14044 and U.S. Pat. Nos. 5,153,157 and 5,453,410 allof which are herein fully incorporated by reference. Also, methods ofactivation such as using radiation and the like are also contemplated asactivators for the purposes of this invention.

[0044] In general the metal compound and the activator are combined inratios of about 1000:1 to about 0.5:1. In a preferred embodiment themetal compound and the activator are combined in a ratio of about 300:1to about 1:1, preferably about 10:1 to about 1:1, for boranes the ratiois preferably about 1:1 to about 10:1 and for alkyl aluminum compounds(such as diethylaluminum chloride combined with water) the ratio ispreferably about 0.5:1 to about 10:1.

[0045] The metal compound and activator are introduced into a slurry orgas phase reactor in a liquid carrier, preferably in solution. Thecatalyst and the activator may be fed in separately or together and maybe combined immediately before being placed in the reactor or may becontacted for longer periods before being placed in the reactor.Preferred liquid carriers include alkanes, preferably pentane, hexane,isopentane, toluene, cyclohexane, isopentane, heptane, octane, isohexaneand the like. Particularly preferred carriers include hexane, pentane,isopentane and toluene.

[0046] The catalyst system, the metal compounds and or the activator arepreferably introduced into the reactor in one or more solutions. In oneembodiment a solution of the activated metal compounds in an alkane suchas pentane, hexane, toluene, isopentane or the like is introduced into agas phase or slurry phase reactor. In another embodiment the catalystsystem or the components can be introduced into the reactor in asuspension or an emulsion. In one embodiment, the transition metalcompound is contacted with the activator, such as modifiedmethylalumoxane, in a solvent and just before the solution is fed into agas or slurry phase reactor. In another embodiment a solution of themetal compound is combined with a solution of the activator, allowed toreact for a period of time then introduced into the reactor. In apreferred embodiment, the catalyst and activator are allowed to reactorfor at least 1 second, preferably at least 5 minutes even morepreferably between 5 and 60 minutes, before being introduced into thereactor. The catalyst and activator are typically present at aconcentration of 0.0001 to 0.200 mol/l in the solutions, preferably0.001 to 0.05 mol/l, more preferably 0.005 to 0.025 mol/l.

[0047] In a preferred embodiment, the catalyst system consists of thetransition metal compound (catalyst) and or the activator (cocatalyst)which are preferably introduced into the reactor in solution. Solutionsof the metal compounds are prepared by taking the catalyst anddissolving it in any solvent such as an alkane, toluene, xylene, etc.The solvent may first be purified in order to remove any poisons whichmay affect the catalyst activity, including any trace water and/oroxygenated compounds. Purification of the solvent may be accomplished byusing activated alumina and activated supported copper catalyst, forexample. The catalyst is preferably completely dissolved into thesolution to form a homogeneous solution. Both catalyst and the activatormay be dissolved into the same solvent, if desired. Once the catalystsare in solution, they may be stored indefinitely until use.

[0048] For polymerization, it preferred that the catalyst is combinedwith an activator prior to injection into the reactor. Additionally,other solvents and reactants can be added to the catalyst solutions(on-line or off-line), to the activator (on-line or off-line), or to theactivated catalyst or catalysts.

[0049] In a preferred embodiment the catalyst systems of this inventionhave a productivity of 10,000 grams of polymer per gram of catalyst perhour or more,

[0050] Polymerization Process of the Invention:

[0051] The catalysts and catalyst systems described above are suitablefor use in the polymerization process of the invention. Thepolymerization process of the invention includes a gas phase or slurryphase process or a combination thereof.

[0052] In an embodiment, this invention is directed toward the slurry orgas phase polymerization or copolymerization reactions involving thepolymerization of one or more monomers having from 2 to 30 carbon atoms,preferably 2-12 carbon atoms, and more preferably 2 to 8 carbon atoms.The invention is particularly well suited to the copolymerizationreactions involving the polymerization of one or more olefin monomers ofethylene, propylene, butene-1, pentene-1,4-methyl-pentene-1, hexene-1,octene-1, decene-1,3-methyl-pentene-1,3,5,5-trimethyl-hexene-1 andcyclic olefins or a combination thereof. Other monomers can includevinyl monomers, diolefins such as dienes, polyenes, norbornene,norbornadiene monomers. Preferably a copolymer of ethylene is produced,where the comonomer is at least one alpha-olefin having from 4 to 15carbon atoms, preferably from 4 to 12 carbon atoms, more preferably from4 to 8 carbon atoms and most preferably from 4 to 7 carbon atoms.

[0053] In another embodiment ethylene or propylene is polymerized withat least two different comonomers to form a terpolymer. The preferredcomonomers are a combination of alpha-olefin monomers having 4 to 10carbon atoms, more preferably 4 to 8 carbon atoms, optionally with atleast one diene monomer. The preferred terpolymers include thecombinations such as ethylene/butene-1/hexene-1,ethylene/propylene/butene-1, propylene/ethylene/hexene-1,ethylene/propylene/norbornene and the like.

[0054] In a particularly preferred embodiment the process of theinvention relates to the polymerization of ethylene and at least onecomonomer having from 3 to 8 carbon atoms, preferably 4 to 7 carbonatoms. Particularly preferred comonomers are butene-1,4-methyl-pentene-1, hexene-1 and octene-1, the most preferred beinghexene-1 and/or butene-1.

[0055] Typically in a gas phase polymerization process a continuouscycle is employed where in one part of the cycle of a reactor system, acycling gas stream, otherwise known as a recycle stream or fluidizingmedium, is heated in the reactor by the heat of polymerization. Thisheat is removed from the recycle composition in another part of thecycle by a cooling system external to the reactor. Generally, in a gasfluidized bed process for producing polymers, a gaseous streamcontaining one or more monomers is continuously cycled through afluidized bed in the presence of a catalyst under reactive conditions.The gaseous stream is withdrawn from the fluidized bed and recycled backinto the reactor. Simultaneously, polymer product is withdrawn from thereactor and fresh monomer is added to replace the polymerized monomer.(See for example U.S. Pat. Nos. 4,543,399, 4,588,790, 5,028,670,5,317,036, 5,352,749, 5,405,922, 5,436,304, 5,453,471, 5,462,999,5,616,661 and 5,668,228 all of which are fully incorporated herein byreference.)

[0056] The reactor pressure in a gas phase process may vary from about10 psig (69 kPa) to about 500 psig (3448 kPa), preferably in the rangeof from about 100 psig (690 kPa) to about 400 psig (2759 kPa),preferably in the range of from about 200 psig (1379 kPa) to about 400psig (2759 kPa), more preferably in the range of from about 250 psig(1724 kPa) to about 350 psig (2414 kPa).

[0057] The reactor temperature in the gas phase process may vary fromabout 30° C. to about 120° C., preferably from about 60° C. to about115° C., more preferably in the range of from about 70° C. to 110° C.,and most preferably in the range of from about 70° C. to about 95° C.

[0058] The productivity of the catalyst or catalyst system is influencedby the main monomer partial pressure. The preferred mole percent of themain monomer, ethylene or propylene, preferably ethylene, is from about25 to 90 mole percent and the monomer partial pressure is in the rangeof from about 75 psia (517 kPa) to about 300 psia (2069 kPa), which aretypical conditions in a gas phase polymerization process.

[0059] In a preferred embodiment, the reactor utilized in the presentinvention and the process of the invention produce greater than 500 lbsof polymer per hour (227 Kg/hr) to about 200,000 lbs/hr (90,900 Kg/hr)or higher of polymer, preferably greater than 1000 lbs/hr (455 Kg/hr),more preferably greater than 10,000 lbs/hr (4540 Kg/hr), even morepreferably greater than 25,000 lbs/hr (11,300 Kg/hr), still morepreferably greater than 35,000 lbs/hr (15,900 Kg/hr), still even morepreferably greater than 50,000 lbs/hr (22,700 Kg/hr) and most preferablygreater than 65,000 lbs/hr (29,000 Kg/hr) to greater than 100,000 lbs/hr(45,500 Kg/hr).

[0060] Other gas phase processes contemplated by the process of theinvention include those described in U.S. Pat. Nos. 5,627,242, 5,665,818and 5,677,375, and European publications EP-A-0 794 200, EP-A-0 802 202and EP-B-634 421 all of which are herein fully incorporated byreference.

[0061] A slurry polymerization process generally uses pressures in therange of from about 1 to about 50 atmospheres and even greater andtemperatures in the range of 0° C. to about 120° C. In a slurrypolymerization, a suspension of solid, particulate polymer is formed ina liquid polymerization diluent medium to which ethylene and comonomersand often hydrogen along with catalyst are added. The suspensionincluding diluent is intermittently or continuously removed from thereactor where the volatile components are separated from the polymer andrecycled, optionally after a distillation, to the reactor. The liquiddiluent employed in the polymerization medium is typically an alkanehaving from 3 to 7 carbon atoms, preferably a branched alkane. Themedium employed should be liquid under the conditions of polymerizationand relatively inert. When a propane medium is used the process must beoperated above the reaction diluent critical temperature and pressure.Preferably, a hexane or an isobutane medium is employed.

[0062] In one embodiment, a preferred polymerization technique of theinvention is referred to as a particle form polymerization, or a slurryprocess where the temperature is kept below the temperature at which thepolymer goes into solution. Such technique is well known in the art, anddescribed in for instance U.S. Pat. No. 3,248,179 which is fullyincorporated herein by reference. The preferred temperature in theparticle form process is within the range of about 185° F. (85° C.) toabout 230° F. (110° C.). Two preferred polymerization methods for theslurry process are those employing a loop reactor and those utilizing aplurality of stirred reactors in series, parallel, or combinationsthereof. Non-limiting examples of slurry processes include continuousloop or stirred tank processes. Also, other examples of slurry processesare described in U.S. Pat. No. 4,613,484, which is herein fullyincorporated by reference.

[0063] In another embodiment, the slurry process is carried outcontinuously in a loop reactor. The catalyst, typically a slurry inisobutane or a solution in an alkane, is injected regularly to thereactor loop, which is itself filled with circulating slurry of growingpolymer particles in a diluent of isobutane containing monomer andcomonomer. Hydrogen, optionally, may be added as a molecular weightcontrol. The reactor is maintained at pressure of about 525 psig to 625psig (3620 kPa to 4309 kPa) and at a temperature in the range of about140° F. to about 220° F. (about 60° C. to about 104° C.) depending onthe desired polymer density. Reaction heat is removed through the loopwall since much of the reactor is in the form of a double-jacketed pipe.The slurry is allowed to exit the reactor at regular intervals orcontinuously to a heated low pressure flash vessel, rotary dryer and anitrogen purge column in sequence for removal of the isobutane diluentand all unreacted monomer and comonomers. The resulting hydrocarbon freepowder is then compounded for use in various applications.

[0064] In an embodiment the reactor used in the slurry process of theinvention is capable of and the process of the invention is producinggreater than 2000 lbs of polymer per hour (907 Kg/hr), more preferablygreater than 5000 lbs/hr (2268 Kg/hr), and most preferably greater than10,000 lbs/hr (4540 Kg/hr). In another embodiment the slurry reactorused in the process of the invention is producing greater than 15,000lbs of polymer per hour (6804 Kg/hr), preferably greater than 25,000lbs/hr (11,340 Kg/hr) to about 100,000 lbs/hr (45,500 Kg/hr).

[0065] In another embodiment in the slurry process of the invention thetotal reactor pressure is in the range of from 400 psig (2758 kPa) to800 psig (5516 kPa), preferably 450 psig (3103 kPa) to about 700 psig(4827 kPa), more preferably 500 psig (3448 kPa) to about 650 psig (4482kPa), most preferably from about 525 psig (3620 kPa) to 625 psig (4309kPa).

[0066] In yet another embodiment in the slurry process of the inventionthe concentration of ethylene in the reactor liquid medium is in therange of from about 1 to 10 weight percent, preferably from about 2 toabout 7 weight percent, more preferably from about 2.5 to about 6 weightpercent, most preferably from about 3 to about 6 weight percent.

[0067] A preferred process of the invention is where the process,preferably a slurry or gas phase process is operated in the absence ofor essentially free of any scavengers, such as triethylaluminum,trimethylaluminum, tri-isobutylaluminum and tri-n-hexylaluminum anddiethyl aluminum chloride, dibutyl zinc and the like. This preferredprocess is described in PCT publication WO 96/08520 and U.S. Pat. No.5,712,352, which are herein fully incorporated by reference.

[0068] In another preferred embodiment the one or all of the catalystsand/or activators are combined with up to 10 weight % of a metalstearate, (preferably a aluminum stearate, more preferably aluminumdistearate) based upon the weight of the catalyst and the stearate,preferably 2 to 3 weight %. In an alternate embodiment a solution of themetal stearate is fed into the reactor. In another embodiment the metalstearate is mixed with the catalyst and fed into the reactor separately.These agents may be mixed with the catalyst or may be fed into thereactor in a solution with or without the catalyst system or itscomponents. In a particularly preferred embodiment a slurry of thestearate in mineral oil is introduced into the reactor separately fromthe metal compounds and or the activators.

[0069] More information on using aluminum stearate type additives may befound in U.S. Ser. No. 09/113,261 filed Jul. 10, 1998, which isincorporated by reference herein.

[0070] The catalyst system of this invention has excellent operabilityover a wide range of reactor conditions and resin grades from 0.2 FlowIndex to 3 Melt Index and 0.950 g/cc to 0.916 g/cc density. The catalystsystem did not experience any resin agglomeration or sheeting in over 10days of continuous pilot scale operation. This invention also has thebenefit of little or no fouling. No sheets, chunks or rubble wereobserved during or after the polymerization process. There was no traceof polymer build-up on the inside of the reactor walls or in the recyclegas line. Also, there was no increase in the pressure drop across theheat exchanger, cycle gas compressor or gas distribution plate duringthe entire run.

[0071] In a preferred embodiment, the polyolefin recovered typically hasa melt index as measured by ASTM D-1238, Condition E, at 190° C. of 3000g/10 min or less, preferably 1000 g/10 min or less, more preferably 20g/10 min or less, more preferably 10 g/l 0 min or less. In a preferredembodiment the polyolefin is ethylene homopolymer or copolymer. In apreferred embodiment for certain applications, such as films, moldedarticle and the like a melt index of 100 g/10 min or less is preferred.For some films and molded article a melt index of 10 g/10 min or less ispreferred. Polyethylene having a melt index of between 0.01 to 10 dg/minis preferably produced. In another preferred embodiment the polymerproduced has a weight average molecular weight of 40,000 Daltons ormore, preferably 60,000 or more, preferably 100,000 or more, preferably120,000 or more, preferably 150,000 or more. For LLDPE cast grade filmsa weight average molecular weight of 40,000 or more is preferred while aweight average molecular weight of 60,000 or more is preferred for blownfilm grades.

[0072] In another embodiment the polymer produced herein has acomposition distribution breadth index (CDBI) of 70 or more, preferably75 or more even more preferably 80 or more. Composition distributionbreadth index is a means of measuring the distribution of comonomerbetween polymer chains in a given sample. CDBI is measured according tothe procedure in WO 93/03093, published Feb. 18, 1993, provided thatfractions having a molecular weight below 10,000 Mn are ignored for thecalculation.

[0073] In a preferred embodiment the catalyst system described above isused to make a polyolefins, preferably polyethylene having a density ofbetween 0.88 and 0.970 g/cm³ (as measured by ASTM 2839). In someembodiments, a density of 0.915 to 0.940 g/cm³ would be preferred, inother embodiments densities of 0.930 to 0.960 g/cm³ are preferred. Inparticular polyethylenes having a density of 0.910 to 0.965, preferably0.915 to 0.960, preferably 0.920 to 0.955 can be produced. In someembodiments, a density of 0.915 to 0.940 g/cm³ would be preferred, inother embodiments densities of 0.930 to 0.970 g/cm³ are preferred.

[0074] In a particularly preferred embodiment the catalyst systemdescribed above is used to make a polyethylene having a density (asmeasured by ASTM D 1505) of 0.910 to 0.935 g/cm³,(preferably 0.915 to0.930 g/cm³), and a melt index (as measured by ASTM D-1238, Condition E,at 190° C.) of 10 or less dg/min, (preferably 5 dg/min or less even morepreferably 3 dg/min or less), giving a film having a haze (as measuredby ASTM 1003-95, Condition A) of 10% or less (preferably 7% or less,even more preferably a 5% or less), and a 450 gloss (as measured by ASTMD 2457) of 60 or more, (preferably 75 or more, more preferably 80 ormore). In an even more preferred embodiment, the polymer is formed intoa film of 0.5 to 10 mil (13 to 250 μm) that has a dart impact (asmeasured by ASTM D 1709, Method A) of 150 g or more, preferably 200 g ormore and an Elmendorf machine direction tear resistance (as measured byASTM D 1922) of 100 g or more preferably 250 g or more, and an Elmendorftransverse direction tear (as measured by ASTM D 1922) of 500 g or more,preferably 600 g or more.

[0075] The polyolefins then can be made into films, molded articles,sheets, pipes, wire and cable coating and the like. The films may beformed by any of the conventional techniques known in the art includingextrusion, co-extrusion, lamination, blowing and casting. The film maybe obtained by the flat film or tubular process which may be followed byorientation in an uniaxial direction or in two mutually perpendiculardirections in the plane of the film to the same or different extents.Orientation may be to the same extent in both directions or may be todifferent extents. Particularly preferred methods to form the polymersinto films include extrusion or coextrusion on a blown or cast filmline.

[0076] The films produced may further contain additives such as slip,antiblock, antioxidants, pigments, fillers, antifog, UV stabilizers,antistats, polymer processing aids, neutralizers, lubricants,surfactants, pigments, dyes and nucleating agents. Preferred additivesinclude silicon dioxide, synthetic silica, titanium dioxide,polydimethylsiloxane, calcium carbonate, metal stearates, calciumstearate, zinc stearate, talc, BaSO₄, diatomaceous earth, wax, carbonblack, flame retarding additives, low molecular weight resins,hydrocarbon resins, glass beads and the like. The additives may bepresent in the typically effective amounts well known in the art, suchas 0.001 weight % to 10 weight %.

EXAMPLES

[0077] Mn and Mw were measured by gel permeation chromatography on awaters 150° C. GPC instrument equipped with differential refractionindex detectors. The GPC columns were calibrated by running a series ofmolecular weight standards and the molecular weights were calculatedusing Mark Houwink coefficients for the polymer is question.

[0078] Density was measured according to ASTM D 1505.

[0079] CDBI (composition distribution breadth index) was measuredaccording to the procedure in WO 93/03093, published Feb. 18, 1993,except that fractions having a molecular weight below 10,000 Mn wereignored for the calculation.

[0080] Melt Index (MI) I₂ and I₂₁ were measured according to ASTMD-1238, Condition E, at 190° C.

[0081] Melt Index Ratio (MIR) is the ratio of I₂₁ over I₂ as determinedby ASTM D-1238.

[0082] Weight % comonomer was measured by proton NMR.

[0083] MWD=Mw/Mn

[0084] 26 inch Dart Impact was measured according to ASTM D 1709, MethodA.

[0085] Elmendorf Tear MD and TD was measured according to ASTM 1922.

[0086] MD and TD 1% Secant modulus were measured according to ASTM D882.

[0087] MD and TD Ultimate Tensile Strength were measured according toASTM D 882.

[0088] MD and TD Ultimate Elongation were measured according to ASTM D412.

[0089] Haze was measured according to ASTM 1003-95, Condition A.

[0090] 45° gloss was measured according to ASTM D 2457.

[0091] MD is Machine Direction, TD is Transverse Direction.

[0092] ESCORENE™ LL3002.32 is a linear low density ethylene-hexenecopolymer produced in a single gas phase reactor using a Ziegler-Nattacatalyst available from Exxon Chemical Company in Houston, Tex., havinga density of 0.918 g/cc, an I₂ of 2 dg/min and having a CDBI(composition distribution breadth index) of less than 65.

[0093] EXCEED™ ECD 125 is a linear low density ethylene-hexene copolymerproduced in a single gas phase reactor using a metallocene catalystavailable from Exxon Chemical Company in Houston, Tex., having a densityof about 0.91 g/cc, an MI of 1.5 g/10 min.

[0094] ESCORENE™ LL3001.63 is a linear low density ethylene-hexenecopolymer produced in a single gas phase reactor using a Ziegler-Nattacatalyst available from Exxon Chemical Company in Houston, Tex., havinga density of 0.918 g/cc, an MI of 1.0 g/10 min.

[0095] EXCEED™350D60 is a linear low density ethylene-hexene copolymerproduced in a single gas phase reactor using a metallocene catalystavailable from Exxon Chemical Company in Houston, Tex., having a densityof 0.918 g/cc, an MI of 1.0 g/10 min and.

[0096] “PPH” is pounds per hour. “mPPH” is millipounds per hour. “ppmw”is parts per million by weight.

[0097] Preparation of Catalyst A

[0098] Preparation of [(2,4,6-Me₃C₆H₂)NHCH₂CH₂]₂NH Ligand (pre-CompoundI)

[0099] A 2 L one-armed Schlenk flask was charged with a magnetic stirbar, diethylenetriamine (23.450 g, 0.227 mol), 2-bromomesitylene (90.51g, 0.455 mol), tris(dibenzylideneacetone)dipalladium (1.041 g, 1.14mmol), racemic-2,2′-bis(diphenylphosphino)-1,1′-binaphthyl (racemicBINAP) (2.123 g, 3.41 mmol), sodium tert-butoxide (65.535 g, 0.682 mol),and toluene (800 mL) under dry, oxygen-free nitrogen. The reactionmixture was stirred and heated to 100° C. After 18 h the reaction wascomplete, as judged by proton NMR spectroscopy. All remainingmanipulations can be performed in air. All solvent was removed undervacuum and the residues dissolved in diethyl ether (1 L). The ether waswashed with water (3×250 mL) followed by saturated aqueous NaCl (180 gin 500 mL) and dried over magnesium sulfate (30 g). Removal of the etherin vacuo yielded a red oil which was dried at 70° C. for 12 h undervacuum (yield: 71.10 g, 92%). ¹H NMR (C₆D₆) d 6.83 (s, 4), 3.39 (br s,2), 2.86 (t, 4), 2.49 (t, 4), 2.27 (s, 12), 2.21 (s, 6), 0.68 (br s, 1).

[0100] Preparation of {[(2,4,6-Me₃C₆H₂)NCH₂CH₂]₂NH}Zr(CH₂Ph)₂ (CompoundI)

[0101] A 500 mL round bottom flask was charged with a magnetic stir bar,tetrabenzyl zirconium (Boulder Scientific) (41.729 g, 91.56 mmol), and300 mL of toluene under dry, oxygen-free nitrogen. Solid pre-compound Iabove (32.773 g, 96.52 mmol) was added with stirring over 1 minute (thedesired compound precipitates). The volume of the slurry was reduced to100 mL and 300 mL of pentane added with stirring. The solidyellow-orange product was collected by filtration and dried under vacuum(44.811 g, 80% yield). ¹H NMR (C₆D₆) d 7.22-6.81 (m, 12), 5.90 (d, 2),3.38 (m, 2), 3.11 (m, 2), 3.01 (m, 1), 2.49 (m, 4), 2.43 (s, 6), 2.41(s, 6), 2.18 (s, 6), 1.89 (s, 2), 0.96 (s, 2).

[0102] Preparation of 1.5 wt % Catalyst A in Toluene Solution

[0103] Note: All procedures below were performed in a glove box.

[0104] 1. Weighed out 100 grams of purified toluene into a 1 LErlenmeyer flask equipped with a Teflon coated stir bar.

[0105] 2. Added 7.28 grams of Tetrabenzyl Zirconium.

[0106] 3. Placed solution on agitator and stirred for 5 minutes. All ofthe solids went into solution.

[0107] 4. Added 5.42 grams of Compound I.

[0108] 5. Added an additional 551 grams of purified toluene and allowedmixture to stir for 15 minutes. No solids remained in the solution.

[0109] 6. Poured catalyst solution into a clean, purged 1-L Whiteysample cylinder, labeled, removed from glovebox and placed in holdingarea for operations.

Example 1

[0110] An ethylene hexene copolymer was produced in a 14-inch (35.6 cm)pilot plant scale gas phase reactor operating at 85° C. and 350 psig(2.4 MPa) total reactor pressure having a water cooled heat exchanger.Ethylene was fed to the reactor at a rate of about 40 pounds per hour(18 kg/hr), hexene was fed to the reactor at a rate of about 0.6 poundsper hour (0.3 kg/hr) and hydrogen was fed to the reactor at a rate of 5mPPH. Nitrogen was fed to the reactor as a make-up gas at about 5-8 PPH.The production rate was about 27 PPH. The reactor was equipped with aplenum having about 1,900 PPH of recycle gas flow. (The plenum is adevice used to create a particle lean zone in a fluidized bed gas-phasereactor. See U.S. Pat. No. 5,693,727.) A tapered catalyst injectionnozzle having a 0.041 inch (0.11 cm) hole size was position in theplenum gas flow. A solution of 1 wt % Catalyst A in toluene andco-catalyst (MMAO-3A, 1 wt % Aluminum in hexane, (MMAO 3A is modifiedmethyl alumoxane in heptane commercially available from Akzo Chemicals,Inc. under the trade name Modified Methylalumoxane type 3A, coveredunder patent number U.S. Pat. No. 5,041,584)) were mixed in line priorto passing through the injection nozzle into the fluidized bed. The MMAOand catalyst were controlled so that the Al:Zr molar ratio was 400:1.Nitrogen and isopentane were also fed to the injection nozzle as neededto maintain a stable average particle size. A unimodal polymer havingnominal 0.28 dg/min (I₂₁) and 0.935 g/cc properties was obtained. Aresidual zirconium of 1.63 ppmw was calculated based on a reactor massbalance.

Example 2

[0111] An ethylene hexene copolymer was produced in a 14-inch (35.6 cm)pilot plant scale gas phase reactor operating at 85° C. and 350 psig(2.4 MPa) total reactor pressure having a water cooled heat exchanger.Ethylene was fed to the reactor at a rate of about 40 pounds per hour(18 kg/hr), hexene was fed to the reactor at a rate of about 3.5 poundsper hour (1.6 kg/hr) and hydrogen was fed to the reactor at a rate of 25mPPH. Nitrogen was fed to the reactor as a make-up gas at about 5-8 PPH.The production rate was about 20 PPH. The reactor was equipped with aplenum having about 1,900 PPH of recycle gas flow. (The plenum is adevice used to create a particle lean zone in a fluidized bed gas-phasereactor. See U.S. Pat. No. 5,693,727.) A tapered catalyst injectionnozzle having a 0.041 inch (0.11 cm) hole size was position in theplenum gas flow. A solution of 1 wt % Catalyst A in toluene, 0.22 PPH of1-hexene and co-catalyst (MMAO-3A, 4 wt % Aluminum in isopentane) weremixed in line prior to passing through the injection nozzle into thefluidized bed. MMAO and catalyst were controlled so that the Al:Zr molarratio was 746:1. Nitrogen and isopentane were also fed to the injectionnozzle as needed to maintain a stable average particle size. A unimodalpolymer having nominal 1.2 dg/min (I₂), 29.7 dg/min (I₂₁), 23.9 I₂₁/I₂ratio and 0.9165 g/cc properties was obtained. A residual zirconium of0.89 ppmw was calculated based on a reactor mass balance.

Example 3

[0112] An ethylene hexene copolymer was produced in a 14-inch (35.6 cm)pilot plant scale gas phase reactor operating at 105° C. and 350 psig(2.4 MPa) total reactor pressure having a water cooled heat exchanger.Ethylene was fed to the reactor at a rate of about 40 pounds per hour(18 kg/hr), hexene was fed to the reactor at a rate of about 0.6 poundsper hour (0.3 kg/hr) and hydrogen was fed to the reactor at a rate of 6mPPH. Nitrogen was fed to the reactor as a make-up gas at about 5-8 PPH.The production rate was about 24 PPH. The reactor was equipped with aplenum having about 1,600 PPH of recycle gas flow. (The plenum is adevice used to create a particle lean zone in a fluidized bed gas-phasereactor. See U.S. Pat. No. 5,693,727.) A tapered catalyst injectionnozzle having a 0.055 inch (0.14 cm) hole size was position in theplenum gas flow. A solution of 1.5 wt % Catalyst A in toluene, andcocatalyst (MMAO-3A, 1.8 wt % Aluminum in 25% heptane/75% hexanesolution) were mixed in line prior to passing through the injectionnozzle into the fluidized bed. MMAO and catalyst were controlled so thatthe Al:Zr molar ratio was 320:1. Nitrogen and isopentane were also fedto the injection nozzle as needed to maintain a stable average particlesize. A unimodal polymer having nominal 0.67 dg/min (I₂₁) and 0.9358g/cc properties was obtained. A residual zirconium of 2.33 ppmw wascalculated based on a reactor mass balance.

Example 4

[0113] An ethylene hexene copolymer was produced in a 14-inch (35.6 cm)pilot plant scale gas phase reactor operating at 85° C. and 350 psig(2.4 MPa) total reactor pressure having a water cooled heat exchanger.Ethylene was fed to the reactor at a rate of about 36 pounds per hour(16.3 kg/hr), hexene was fed to the reactor at a rate of about 3.5pounds per hour (1.6 kg/hr) and hydrogen was fed to the reactor at arate of 28 mPPH. Nitrogen was fed to the reactor as a make-up gas atabout 5-8 PPH. The production rate was about 18 PPH. The reactor wasequipped with a plenum having about 1,900 PPH of recycle gas flow. (Theplenum is a device used to create a particle lean zone in a fluidizedbed gas-phase reactor. See U.S. Pat. No. 5,693,727.) A tapered catalystinjection nozzle having a 0.041 inch (0.11 cm) hole size was position inthe plenum gas flow. A solution of 1 wt % Catalyst A in toluene, 0.22PPH of 1-hexene and cocatalyst (MMAO-3A, 4 wt % Aluminum in isopentane)were mixed in line prior to passing through the injection nozzle intothe fluidized bed. MMAO and catalyst were controlled so that the Al:Zrmolar ratio was 925:1. Nitrogen and isopentane were also fed to theinjection nozzle as needed to maintain a stable average particle size. Aunimodal polymer having nominal 1.7 dg/min (I₂), 41.7 dg/min (I₂₁), 24.1I₂₁/I₂ and 0.917 g/cc properties was obtained. A residual zirconium of0.94 ppmw was calculated based on a reactor mass balance.

Example 5

[0114] An ethylene hexene copolymer was produced in a 14-inch (35.6 cm)pilot plant scale gas phase reactor operating at 85° C. and 350 psig(2.4 MPa) total reactor pressure having a water cooled heat exchanger.Ethylene was fed to the reactor at a rate of about 40 pounds per hour(18 kg/hr), hexene was fed to the reactor at a rate of about 0.6 poundsper hour (0.3 kg/hr) and hydrogen was fed to the reactor at a rate of3.5 mPPH. Nitrogen was fed to the reactor as a make-up gas at about 5-8PPH. The production rate was about 22 PPH. The reactor was equipped witha plenum having about 1,500 PPH of recycle gas flow. (The plenum is adevice used to create a particle lean zone in a fluidized bed gas-phasereactor. See U.S. Pat. No. 5,693,727.) A tapered catalyst injectionnozzle having a 0.041 inch (0.11 cm) hole size was position in theplenum gas flow. A solution of 1 wt % Catalyst A in toluene andcocatalyst (MMAO-3A, 1 wt % Aluminum in hexane) were mixed in line priorto passing through the injection nozzle into the fluidized bed. MMAO andcatalyst were controlled so that the Al:Zr molar ratio was 450:1.Nitrogen and isopentane were also fed to the injection nozzle as neededto maintain a stable average particle size. A unimodal polymer havingnominal 0.10 dg/min (I₂₁) and 0.931 g/cc properties was obtained. Aresidual zirconium of 1.36 ppmw was calculated based on a reactor massbalance.

Example 6

[0115] An ethylene hexene copolymer was produced in a 14-inch (35.6 cm)pilot plant scale gas phase reactor operating at 85° C. and 350 psig(2.4 MPa) total reactor pressure having a water cooled heat exchanger.Ethylene was fed to the reactor at a rate of about 40 pounds per hour(18 kg/hr), hexene was fed to the reactor at a rate of about 0.5 poundsper hour (0.23 kg/hr) and hydrogen was fed to the reactor at a rate of 4mPPH. Nitrogen was fed to the reactor as a make-up gas at about 5-8 PPH.The production rate was about 20 PPH. The reactor was equipped with aplenum having about 2,050 PPH of recycle gas flow. (The plenum is adevice used to create a particle lean zone in a fluidized bed gas-phasereactor. See U.S. Pat. No. 5,693,727.) A tapered catalyst injectionnozzle having a 0.041 inch (0.11 cm) hole size was position in theplenum gas flow. A solution of 1 wt % Catalyst A in toluene andcocatalyst (MMAO-3A, 4 wt % Aluminum in isopentane) were mixed in lineprior to passing through the injection nozzle into the fluidized bed.MMAO and catalyst were controlled so that the Al:Zr molar ratio was1550:1. Nitrogen and isopentane were also fed to the injection nozzle asneeded to maintain a stable average particle size. A unimodal polymerhaving nominal 0.36 dg/min (I₂₁) and 0.943 g/cc properties was obtained.A residual zirconium of 2.5 ppmw was calculated based on a reactor massbalance.

Example 7

[0116] An ethylene hexene copolymer was produced in a 14-inch (35.6 cm)pilot plant scale gas phase reactor operating at 85° C. and 350 psig(2.4 MPa) total reactor pressure having a water cooled heat exchanger.Ethylene was fed to the reactor at a rate of about 40 pounds per hour(18 kg/hr), hexene was fed to the reactor at a rate of about 0.6 poundsper hour (0.3 kg/hr) and hydrogen was fed to the reactor at a rate of 12mPPH. Nitrogen was fed to the reactor as a make-up gas at about 5-8 PPH.The production rate was about 20 PPH. The reactor was equipped with aplenum having about 2,050 PPH of recycle gas flow. (The plenum is adevice used to create a particle lean zone in a fluidized bed gas-phasereactor. See U.S. Pat. No. 5,693,727.) A tapered catalyst injectionnozzle having a 0.041 inch (0.11 cm) hole size was position in theplenum gas flow. A solution of 1 wt % Catalyst A in toluene andcocatalyst (MMAO-3A, 4 wt % Aluminum in isopentane) were mixed in lineprior to passing through the injection nozzle into the fluidized bed.MMAO and catalyst were controlled so that the Al:Zr molar ratio was868:1. Nitrogen and isopentane were also fed to the injection nozzle asneeded to maintain a stable average particle size. A unimodal polymerhaving nominal 3.5 dg/min (I₂₁), 0.115 dg/min (I₂), 30.2 I₂₁/I₂ ratioand 0.949 g/cc properties was obtained. A residual zirconium of 2.5 ppmwwas calculated based on a reactor mass balance.

Example 8

[0117] An ethylene hexene copolymer was produced in a 14-inch (35.6 cm)pilot plant scale gas phase reactor operating at 85° C. and 350 psig(2.4 MPa) total reactor pressure having a water cooled heat exchanger.Ethylene was fed to the reactor at a rate of about 40 pounds per hour(18 kg/hr), hexene was fed to the reactor at a rate of about 1.1 poundsper hour and hydrogen was fed to the reactor at a rate of 12 mPPH.Nitrogen was fed to the reactor as a make-up gas at about 5-8 PPH. Theproduction rate was about 25 PPH. The reactor was equipped with a plenumhaving about 1,900 PPH of recycle gas flow. (The plenum is a device usedto create a particle lean zone in a fluidized bed gas-phase reactor. SeeU.S. Pat. No. 5,693,727.) A tapered catalyst injection nozzle having a0.041 inch (0.11 cm) hole size was position in the plenum gas flow. Asolution of 1 wt % Catalyst A in toluene and cocatalyst (MMAO-3A, 4 wt %Aluminum in isopentane) were mixed in line prior to passing through theinjection nozzle into the fluidized bed. MMAO and catalyst werecontrolled so that the Al:Zr molar ratio was 842:1. Nitrogen andisopentane were also fed to the injection nozzle as needed to maintain astable average particle size. A unimodal polymer having nominal 41.2dg/min (I₂₁), 1.22 dg/min (I₂), 33.8 I₂₁/I₂ ratio and 0.940 g/ccproperties was obtained. A residual zirconium of 2.77 ppmw wascalculated based on a reactor mass balance.

Example 9

[0118] An ethylene hexene copolymer was produced in a 14-inch (35.6 cm)pilot plant scale gas phase reactor operating at 90° C. and 350 psig(2.4 MPa) total reactor pressure having a water cooled heat exchanger.Ethylene was fed to the reactor at a rate of about 48 pounds per hour,hexene was fed to the reactor at a rate of about 0.6 pounds per hour(0.3 kg/hr) and hydrogen was fed to the reactor at a rate of 10 mPPH.Nitrogen was fed to the reactor as a make-up gas at about 5-8 PPH. Theproduction rate was about 23 PPH. The reactor was equipped with a plenumhaving about 1,600 PPH of recycle gas flow. (The plenum is a device usedto create a particle lean zone in a fluidized bed gas-phase reactor. SeeU.S. Pat. No. 5,693,727.) A tapered catalyst injection nozzle having a0.055 inch (1.4 cm) hole size was position in the plenum gas flow. Asolution of 1.5 wt % Catalyst A in toluene, and cocatalyst (MMAO-3A, 1.8wt % Aluminum in 25%heptane/75%hexane) were mixed in line prior topassing through the injection nozzle into the fluidized bed. MMAO andcatalyst were controlled so that the Al:Zr molar ratio was 265:1.Nitrogen and isopentane were also fed to the injection nozzle as neededto maintain a stable average particle size. A unimodal polymer havingnominal 0.3 dg/min (I₂₁) and 0.933 g/cc properties was obtained. Aresidual zirconium of 2.38 ppmw was calculated based on a reactor massbalance.

Example 10

[0119] An ethylene hexene copolymer was produced in a 14-inch (35.6 cm)pilot plant scale gas phase reactor operating at 95° C. and 350 psig(2.4 MPa) total reactor pressure having a water cooled heat exchanger.Ethylene was fed to the reactor at a rate of about 45 pounds per hour,hexene was fed to the reactor at a rate of about 0.6 pounds per hour(0.3 kg/hr) and hydrogen was fed to the reactor at a rate of 6 mPPH.Nitrogen was fed to the reactor as a make-up gas at about 5-8 PPH. Theproduction rate was about 25 PPH. The reactor was equipped with a plenumhaving about 1,600 PPH of recycle gas flow. (The plenum is a device usedto create a particle lean zone in a fluidized bed gas-phase reactor. SeeU.S. Pat. No. 5,693,727.) A tapered catalyst injection nozzle having a0.055 inch (1.4 cm) hole size was position in the plenum gas flow. Asolution of 1.5 wt % Catalyst A in toluene, and cocatalyst (MMAO-3A, 1.8wt % Aluminum in 25% heptane/75% hexane) were mixed in line prior topassing through the injection nozzle into the fluidized bed. MMAO andcatalyst were controlled so that the Al:Zr molar ratio was 350:1.Nitrogen and isopentane were also fed to the injection nozzle as neededto maintain a stable average particle size. A unimodal polymer havingnominal 0.4 dg/min (I₂₁) and 0.934 g/cc properties was obtained. Aresidual zirconium of 2.27 ppmw was calculated based on a reactor massbalance.

[0120] The data for examples 1-10 are summarized in Table 1. TABLE 1 I₂Resid- EXAM- Temp. dg/ I₂₁ Density ual Zr PLE ° C. H₂/C₂ C₆/C₂ mindg/min g/cc ppmw 1 85 0.0015 0.0043 n/a 0.28 0.935 1.63 2 85 0.0080.0410 1.2 29.7 0.9165 0.89 3 105 0.0015 0.0050 n/a 0.67 0.9358 2.33 485 0.0087 0.0405 1.7 41.7 0.917 0.94 5 85 0.0006 0.0051 n/a 0.1 0.9311.36 6 85 0.0023 0.0012 n/a 0.36 0.943 2.50 7 85 00051 0.0013 0.115 3.50.949 2.50 8 85 0.0114 0.0154 1.22 41.2 0.940 2.77 9 90 0.0015 0.0050n/a 0.3 0.933 2.38 10 95 0.0015 0.0050 n/a 0.4 0.934 2.27

Example 11

[0121] 300 pounds (138 kg) of polyethylene produced according to example4 above (referred to as Polymer A) was compounded on a Werner-FleidererZSK-30 twin screw extruder with 1000 ppm Irganox™ 1076 and 1500 ppmIrgafos™ 1068 at a melt temperature of 200° C. and formed into pellets.Then the pellets were blown into a 1.0 mil (25 μm) film on an Gloucesterblown film extrusion line at 188 lb/hr (85 kg/hr) rate, at 390° F. (199°C.) melt temperature, 24 inch (61 cm) frostline height, 2.5 blow-upratio, and 60 mil (1524 μm) die gap. ESCORENE™ HD7755.10 (a conventionalseries reactor product of Exxon Chemical Company in Mt. Belvue Tex.) wasrun at the same conditions as a comparison. All films were conditionedaccording to 23° C., 50% humidity for 40 hours. The data are presentedin Tables 2 and 3. TABLE 2 Polymer A Escorene ™ 1.8 g/10 min Escorene ™Example LL3002.32 MI LL3001.63 I₂, g/10 min 2 1076 1 I₂₁/I₂ 29 24 27Pellet density g/cc 0.918 0.918 0.918 Head Pressure psi (MPa) 2690 (19)2470 (17) 3380 (23) Motor load, % 43 31.2 50.4 Film gage mil, (μm) 1(25) 1 (25) 1 (25) Film Density, g/cc 0.917 0.916 0.917 26 inch (66 cm)Dart, g 136 168 149 Elm. Tear g/mil (g/μm) MD 310(12.7) 254(10.4)223(9.1) Elm. Tear g/mil (g/μm) TD 609(24.9) 630(25.7) 753(30.7) 1%Secant Mod. psi 30430 (210) 31580 (218) 31320 (216) (MPa) MD 1% SecantMod. psi 38950 (269) 42120 (2902) 39750 (274) (MPa) TD Ult. Tensile Str.psi 7444 (51) 8551 (59) 8880 (61) (MPa) MD Ult. Tensile Str. psi 6498(45) 9892 (68) 6894 (48) (MPa) TD Ultimate Elongation % MD 641 546 552Ultimate Elongation % TD 793 694 756 45° gloss 40 79 23 Haze % 22 4.4 20

[0122] TABLE 3 Polymer A EXCEED ™ Example 1.3 MI 350D60 I₂, g/10 min1.35 1 I₂₁/I₂ 23 16 Pellet density g/cc 0.918 0.918 Head Pressure psi(MPa) 3010 (21) 3810 (26) Motor load, % 37.2 56.7 Film gage mil, (μm) 1(25) 1 (25) Film Density, g/cc 0.916 0.916 26 inch (66 cm) Dart, g 276646 Elm. Tear g/mil (g/μm) MD 219? 264? Elm. Tear g/mil (g/μm) TD 616?392? 1% Secant Mod. psi 31100 (214) 29040 (200) (MPa) MD 1% Secant Mod.psi 41470 (286) 33050 (228) (MPa) TD Ult. Tensile Str. psi 9017 (62)9986 (69) (Mpa) MD Ult. Tensile Str. psi 7684 (53) 8535 (59) (MPa) TDUltimate Elongation % MD 529 504 Ultimate Elongation % TD 690 646 45°gloss 74 25 Haze % 5 23

[0123] All documents described herein are incorporated by referenceherein, including any priority documents and/or testing procedures. Asis apparent form the foregoing general description and the specificembodiments, while forms of the invention have been illustrated anddescribed, various modifications can be made without departing from thespirit and scope of the invention. Accordingly it is not intended thatthe invention be limited thereby.

1. A composition comprising polyethylene having a density of 0.190 g/ccto 0.935 g/cc and a melt index of 10 dg/min or less, a haze of 10% orless and a 45° gloss of 60 units or more.
 2. The composition of claim 1wherein the polyethylene has a density of 0.915-0.930 g/cc.
 3. Thecomposition of claim 1 wherein the polyethylene has a melt index of 5dg/min or less.
 4. The composition of claim 1 wherein the polyethylenehas a melt index of 3 dg/min or less.
 5. The composition of claim 1wherein the polyethylene has a haze of 7% or less.
 6. The composition ofclaim 1 wherein the polyethylene has a haze of 5% or less.
 7. Thecomposition of claim 1 wherein the polyethylene has a 45° gloss of 75units or more.
 8. The composition of claim 1 wherein the polyethylenehas a 45° gloss of 80 units or more.
 9. The composition of claim 1wherein the polyethylene has a dart impact of 150 g or more (as measuredby ASTM D 1709 Method A) and an Elmendorf tear of 100 g or more in themachine direction and an Elmendorf tear of 500 g or more in thetransverse direction.
 10. The composition of claim 1 wherein thepolyethylene has a dart impact of 150 g or more (as measured by ASTM1709, Method A).
 11. The composition of claim 1 wherein the polyethylenehas an Elmendorf tear of 100 g or more in the machine direction.
 12. Thecomposition of claim 1 wherein the polyethylene has an Elmendorf tear of500 g or more in the transverse direction.